CN104628944B - Acrylamide copolymer, as well as preparation method and application thereof - Google Patents
Acrylamide copolymer, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an acrylamide copolymer, as well as a preparation method and an application thereof. The copolymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a unit having a structure as shown in a formula (1), the structural unit B is at least one unit having a structure as shown in formulae from (2) to (5), and the structural unit C is a unit having a structure as shown in a formula (6); the mass ratio of the structural unit A to structural unit B to structural unit C is 1:(0.001-3):(0.001-0.5); and the viscosity-average molecular weight of the acrylamide copolymer is 31-39 millions. A temperature-resistance salt-resistance product prepared from the acrylamide copolymer has the characteristics of good water solubility, low content of residual monomer, high molecular weight and high apparent viscosity, and can be used as an oil-displacing agent for tertiary recovery of a high temperature and high salinity reservoir.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and its preparation method and application.
Background technology
Polymer flooding mainly passes through to inject the polymer solution of certain scale, increases displacement fluid viscosity, reduces oil-reservoir water
Phase permeability, to reduce mobility ratio, adjustment intake profile, to reach the purpose improving displacement phase volume, and then improves recovery ratio.
As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA)（HPAM）In conventional oil reservoir tertiary oil recovery (EOB) technology,
Obtain large-scale promotion and application, be oilfield stable production and volume increase has played important function.With subtracting of conventional reservoir reserve
Few, high temperature and high salt oil deposit makes the application of HPAM be faced with many difficult problems, is mainly reflected in height during exploitation high temperature and high salt oil deposit
The compound action that in temperature, high salt and solution, dissolved oxygen produces makes HPAM solution viscosity be greatly reduced, and leads to HPAM oil displacement efficiency
Not notable.Research shows, when temperature is higher than 70 DEG C, the acylamino- hydrolysis of HPAM generate carboxyl significantly to be aggravated, and works as degree of hydrolysis
Reach more than 40%, carboxyl is just easy to and Ca in solution2+、Mg2+Ion generates precipitation, so that solution viscosity is lost.Additionally, in height
Under temperature, when there is dissolved oxygen in the air oxygen and solution, main polymer chain fracture also can be caused so that solution viscosity is remarkably decreased.
In order to improve the temperature-resistant anti-salt performance of polyacrylamide, a large amount of tackling key problem researchs are carried out both at home and abroad, mainly around poly-
The chain yardstick of compound, chain size distribution, construction unit composition, micro-sequential structure carry out a large amount of correlational study work, such as heatproof
Salt resistance monomer-polymer, hydrophobic associated polymer, amphiphilic polymers, composite polymer, comb polymer, template polymer and
Surface-active polymer etc..As entitled " the low temperature synthesis of AMPS/AM copolymer and performance "（Chang Zhiying, polymer material science
With engineering, 1997,13,16）With acrylamide (AM) and heat-resistant salt-resistant monomer 2- acrylamide-2-methylpro panesulfonic acid (AMPS)
Copolymerization bipolymer；CN200810015349.7 discloses a kind of comb-type structure activity polymer and its preparation technology and answers
With by polyurethaness surface-active macromonomer with monomers such as acrylamides altogether
Aggregate into tackifying and reduce interfacial tension target product.The polymer that above two method obtains respectively has it
Feature, in some performances such as temperature tolerance, salt-resistance, shear resistant and surface activity index, more traditional polyacrylamide is really
Increase, but it is little to obtain molecular weight of product（Less than 20,000,000）, lead to the use of polymer to be restricted.
Content of the invention
It is an object of the invention to overcoming the drawbacks described above of prior art, provide a kind of acrylamide copolymer and its preparation
Methods and applications.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains construction unit A, construction unit
B and construction unit C, wherein, described construction unit A is to have formula（1）The unit of shown structure, described construction unit B is to have
Formula（2）- formula（5）At least one in the unit of shown structure, described construction unit C is to have formula（6）The unit of shown structure,
And the mass ratio of described construction unit A, described construction unit B and described construction unit C is 1：0.001-3：0.001-0.5, excellent
Elect 1 as：0.01-1.5：0.01-0.2；The viscosity-average molecular weight of described acrylamide copolymer is 31,000,000-3,900 ten thousand, preferably
34000000-3,800 ten thousand,
Wherein, R1、R2、R6、R7、R10、R11And R12It is each independently the alkyl of hydrogen or C1-C4, R3Alkylene for C1-C14
Base；R4、R5、R8、R9And R13It is each independently the alkyl of C1-C4, R14Alkyl for C1-C18, M1And M2It is each independently
At least one in H, Na and K, n is arbitrary integer in 1-20, and m is arbitrary integer in 1-20.
Present invention also offers a kind of preparation method of acrylamide copolymer, this preparation method comprises the following steps,
Under the conditions of solution polymerization, in the presence of initiator, a kind of monomer mixture is made to carry out polyreaction, wherein, institute in water
State monomer mixture and contain monomer E, monomer F and monomer G, described monomer E is to have formula（8）The monomer of shown structure, described list
Body F is to have formula（9）- formula（12）At least one in the monomer of shown structure, described monomer G is to have formula（13）Shown structure
Monomer, and the mass ratio of described monomer E, described monomer F and described monomer G be 1：0.001-3：0.001-0.5, preferably 1：
0.01-1.5：0.01-0.2；After described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is
31000000-3,900 ten thousand, preferably 34,000,000-3,800 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10’、R11' and R12' it is each independently the alkyl of hydrogen or C1-C4, R3' it is C1-C14
Alkylidene；R4’、R5’、R8’、R9' and R13' it is each independently the alkyl of C1-C4, R14' for C1-C18 alkyl, M1' and
M2' it is each independently at least one in H, Na and K, n ' is arbitrary integer in 1-20, and m ' is arbitrary integer in 1-20.
The main chain of the acrylamide copolymer strand of the present invention is mainly by acrylamide and temperature-resistant anti-salt monomer structure list
Unit is constituted, and is ensureing polymeric water-soluble simultaneously, can improve temperature-resistant anti-salt and the anti-shear performance of polymer molecule.Copolymer
Side chain is made up of surface active function monomer, has generation Interpolymer Association effect, increases the slack time of molecular motion, improve
Solution viscoelasticity and reduction oil water interfacial tension effect.
Using the temperature-resistant anti-salt product of the acrylamide copolymer of the present invention have water-soluble good, residual monomer content low and point
The high feature of son amount.The acrylamide copolymer molecular weight of the present invention up to more than 33,000,000, particularly in salinity
Under 32000mg/L, 95 DEG C of hot conditionss, the apparent viscosity of solution is up to more than 20mPa.s, and commercially available high molecular weight polypropylene
Only 20,000,000 about, the apparent viscosity of solution is only 8.9mPa.s to the molecular weight of amide, compared with commercially available prod, the propylene of the present invention
Amide copolymer has significantly thickening advantage, can be used as high temperature and high salt oil deposit Flooding Agent for EOR.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains construction unit A, construction unit
B and construction unit C, wherein, described construction unit A is to have formula（1）The unit of shown structure, described construction unit B is to have
Formula（2）- formula（5）At least one in the unit of shown structure, described construction unit C is to have formula（6）The unit of shown structure,
And the mass ratio of described construction unit A, described construction unit B and described construction unit C is 1：0.001-3：0.001-0.5, excellent
Elect 1 as：0.01-1.5：0.01-0.2；The viscosity-average molecular weight of described acrylamide copolymer is 31,000,000-3,900 ten thousand, preferably
34000000-3,800 ten thousand,
Wherein, R1、R2、R6、R7、R10、R11And R12It is each independently the alkyl of hydrogen or C1-C4, R3Alkylene for C1-C14
Base；R4、R5、R8、R9And R13It is each independently the alkyl of C1-C4, R14Alkyl for C1-C18, M1And M2It is each independently
At least one in H, Na and K, n is arbitrary integer in 1-20, and m is arbitrary integer in 1-20.
In the present invention, the alkyl of described C1-C4 can be straight chain or side chain.The alkyl of described C1-C4
Example can include：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
In the present invention, the alkyl of described C1-C18 can be straight chain or side chain.The alkane of described C1-C18
The example of base can include but is not limited to：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group,
N-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive ten
Diyl, positive tritriacontyl, positive tetradecyl, positive pentadecyl, positive palmityl, positive heptadecyl and positive octadecyl.
In the present invention, the alkylidene of described C1-C14 can be straight or branched, the reality of the alkylidene of described C1-C14
Example can include but is not limited to：Methylene, ethylidene, sub- n-pro-pyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene
With the sub- tert-butyl group, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, Asia
N-nonyl, sub- positive decyl, sub- positive hendecyl, sub- positive dodecyl, sub- positive tritriacontyl and sub- positive tetradecyl.Described alkylidene refers to alkane
Hydrocarbon loses the residue after two hydrogen atoms, and described two hydrogen atoms can be two hydrogen atoms on same carbon atom, also may be used
With two hydrogen atoms on different carbon atoms, can be straight chain or side chain, for example, described ethylidene can be-
CH2CH2- or-CH (CH3)-.
In the present invention, although as long as containing construction unit A, construction unit B and construction unit C and meet aforementioned proportion pass
System can achieve the purpose of the present invention, but under preferable case, the amount of construction unit A accounts for the 30-99 of described acrylamide copolymer
Weight %.
According to the present invention, described acrylamide based copolymer also contains construction unit D, and described construction unit D is to have formula
（7）The unit of shown structure：
Wherein, M3For potassium or sodium, preferably sodium.
The present invention does not specially require to the quality of construction unit D, for instance, it is preferred that described construction unit A, described knot
The mass ratio of structure unit B, described construction unit C and described construction unit D is 1：0.001-3：0.001-0.5：0.1-1, enters one
Step is preferably 1：0.01-1.5：0.01-0.2：0.1-1.
The present inventor finds under study for action, by specific construction unit A, construction unit B, construction unit C and knot
Preferable oil displacement efficiency can be obtained good when the quadripolymer of structure cells D composition is for oil displacement agent.For instance, it is preferred that described knot
Structure unit B is to have formula（2）With（4）At least one in the unit of shown structure, and R2And R7It is each independently hydrogen or first
Base, R3Alkylidene for C1-C4, M1For sodium；In described construction unit C, R13For methyl, R14Alkyl for C5-C18, M2For sodium,
N is the arbitrary integer in 8-12, and when m is the arbitrary integer in 2-8, the quadripolymer of composition is used for taking during oil displacement agent
Obtain preferable oil displacement efficiency.It is further preferred that described construction unit C is to have formula（14）The unit of shown structure,
Wherein, R14Straight chained alkyl for C8-C16.
Present invention also offers a kind of preparation method of acrylamide copolymer, this preparation method comprises the following steps,
Under the conditions of solution polymerization, in the presence of initiator, a kind of monomer mixture is made to carry out polyreaction, wherein, institute in water
State monomer mixture and contain monomer E, monomer F and monomer G, described monomer E is to have formula（8）The monomer of shown structure, described list
Body F is to have formula（9）- formula（12）At least one in the monomer of shown structure, described monomer G is to have formula（13）Shown structure
Monomer, and the mass ratio of described monomer E, described monomer F and described monomer G be 1：0.001-3：0.001-0.5, preferably 1：
0.01-1.5：0.01-0.2；After described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is
31000000-3,900 ten thousand, preferably 34,000,000-3,800 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10’、R11' and R12' it is each independently the alkyl of hydrogen or C1-C4, R3' it is C1-
The alkylidene of C14；R4’、R5’、R8’、R9' and R13' it is each independently the alkyl of C1-C4, R14' for C1-C18 alkyl, M1’
And M2' it is each independently at least one in H, Na and K, n ' is arbitrary integer in 1-20, and m ' is arbitrarily whole in 1-20
Number.
The alkyl of described C1-C4, the alkylidene of C1-C14 are all identical with foregoing description with the alkyl of C1-C18.
In the present invention, monomer E is preferably 40-99 weight % of monomer mixture gross mass.
The present inventor finds under study for action, when selecting specific monomer E, monomer F and monomer G to be reacted,
The oil displacement efficiency of the polymer of gained can be improved further.For instance, it is preferred that when described monomer F is to have formula（9）And formula
（11）At least one in the monomer of shown structure, and R2' and R7' it is each independently hydrogen or methyl, R3' for C1-C4 alkylene
Base, M1' it is sodium；In described monomer G, R13' it is methyl, R14' for C5-C18 alkyl, M2' it is sodium, n ' is arbitrary in 8-12
Integer, when m ' is the arbitrary integer in 2-8, the polymer of synthesis has higher oil displacement efficiency, it is further preferred that institute
Stating monomer G is to have formula（15）The monomer of shown structure：
Wherein, R14' for C8-C16 straight chained alkyl.
In the present invention, described monomer G can the method according to CN101327413A be obtained：For example, 1）First will
Maleic anhydride is reacted from the fat alcohol polyethylene ether of different ethoxymer distributions, feeds intake by equimolar ratio, heated and stirred is to horse
Carry out anhydride fusing, react 2-5 hour at 70-100 DEG C, reaction obtains maleic acid list polyoxyethylene ether-ester after terminating；2）By Malaysia
Acid list polyoxyethylene ether-ester is heated to 40-80 DEG C, Deca acyl chlorides reagent Phosphorous chloride., and both mol ratios are 1：0.5-3,
40-80 DEG C carries out acyl chloride reaction, obtains fatty alcohol-polyoxyethylene ether monoesters fumaryl chloride；3）Water by N methyl taurine sodium
It is 8-10 that solution adjusts pH value with concentrated hydrochloric acid under the conditions of 50-80 DEG C, will be slow for fatty alcohol-polyoxyethylene ether monoesters fumaryl chloride
It is added drop-wise in the aqueous solution of N methyl taurine sodium, react 1-3 hour, that is, obtain the monomer G of the present invention.
According to the present invention, described solution polymerization is carried out in water, when described solution polymerization starts, described monomer
There is no particular limitation for the ratio of the gross weight of the weight of mixture and water and monomer mixture, can become in wider scope
Dynamic, under preferable case, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.15-0.4：1,
More preferably 0.2-0.3：1.
In the present invention, described initiator can be the various initiator in this area.For example, described initiator can be selected from even
Nitrogen series initiators and/or oxidoreduction body class initiator, preferably azo series initiators and oxidoreduction body class initiator.Described
The consumption of azo series initiators is 0.0001-0.1 weight % of the gross weight of monomer in monomer mixture, preferably 0.001-
0.05 weight %；The consumption of described oxidoreduction series initiators is the 0.0002-0.3 weight of the gross weight of monomer in monomer mixture
Amount %, preferably 0.002-0.15 weight %.Described azo series initiators are preferably water-soluble azo series initiators, and described oxidation is also
Former series initiators include Oxidizing and Reducing Agents, and described reducing agent is inorganic reducing agent and/or organic reducing agent, and described oxidation
The weight of agent and described reducing agent is than for 0.1-1:1.
In the present invention, described water-soluble azo series initiators be preferably 2,2'- azo diisobutyl amidine dihydrochloride, 2,
At least one in 2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride and 4,4'- azo double (4- cyanopentanoic acid),
More preferably 2,2'- azo diisobutyl amidine dihydrochloride.
In the present invention, described oxidant can be selected from least in acyl peroxide, hydroperoxides and persulfate
Kind, preferably benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5 pairs of (hydrogen peroxide) hexanes,
At least one in Ammonium persulfate., sodium peroxydisulfate and potassium peroxydisulfate, more preferably Ammonium persulfate. and/or potassium peroxydisulfate.
In the present invention, described reducing agent can be inorganic reducing agent and/or organic reducing agent, preferably inorganic reducing agent
And organic reducing agent.Described inorganic reducing agent can be selected from ferrous sulfate, Ferrous ammonium sulfate, Cu-lyt., potassium sulfite, sulfurous
In sour sodium, ammonium bisulfite, Potassium acid sulfite, sodium thiosulfate, Potassium hyposulfite., rongalite and sodium sulfite at least one
Kind, preferably sodium sulfite；Described organic reducing agent is preferably amine reducing agent, and described amine reducing agent is preferably N, N- bis-
Methylethanolamine, N, N- lupetazin, tetramethylurea and N, N, N ', at least one in N '-tetramethylethylenediamine, further
It is preferably N, N, N ', N '-tetramethylethylenediamine.
According to the present invention, the condition of described solution polymerization can be the conventional condition in this area.For example, described polymerization
Reaction is carried out in the presence of an inert gas, and described polymeric reaction condition can include：Temperature is -10 DEG C to 20 DEG C, and preferably 5 DEG C extremely
15℃；Time is 2-12 hour, preferably 4-8 hour；PH value is 4-12, preferably 5-10.
Described noble gases are the gas not reacted with raw material and product, for example, can be the conventional nitrogen in this area
Or at least one in group 0 element gas in the periodic table of elements, preferably nitrogen.
According to the present invention, methods described also includes resulting polymers after polyreaction being hydrolyzed and being dried.This area
Technical staff could be aware that, the process of hydrolysis is included hydrolytic reagent and polymer reaction.By hydrolysis, part propylene acyl
Amine structure unit is formula（1）Shown construction unit is transformed into acrylates construction unit, i.e. formula（7）Shown structure
Unit.
In the present invention, the condition of described hydrolysis is not particularly limited, under preferable case, the condition bag of described hydrolysis
Include：Temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hour, preferably 1-4 hour；Described hydrolysis makes poly-
The degree of hydrolysis closing resulting polymers after reacting can be 10-30%.
In the present invention, described degree of hydrolysis refers to that the molal quantity of acrylates construction unit accounts for the acrylamide of the present invention altogether
The percentage ratio of the total mole number of the construction unit of polymers.Described degree of hydrolysis is determined by the consumption of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkaline compounds being capable of above-mentioned purpose commonly used in the art,
Can be selected from one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.The consumption of described hydrolytic reagent can be according to propylene
The degree of hydrolysis of amide copolymer carries out suitable selection, so that the degree of hydrolysis of acrylamide copolymer meets use requirement being defined,
It is 10-30% that the consumption of preferably inorganic alkaline compound makes the degree of hydrolysis of acrylamide copolymer.
Those skilled in the art could be aware that, by adjusting the consumption of inorganic alkaline compound, can obtain not
Acrylamide copolymer with degree of hydrolysis.
In the present invention, the molal quantity of described inorganic alkaline compound is equal to the molal quantity of acrylates construction unit.
According to the present invention, the present invention can adopt hot-air seasoning to drying condition no particular/special requirement, described drying meanss,
Described hot air drying temperature can be 40-120 DEG C, preferably 70-90 DEG C；Time is 0.2-4 hour, preferably 0.5-2 hour.
The present invention one kind preferred embodiment in, the preparation method of described acrylamide copolymer includes walking as follows
Suddenly：
（1）Acrylamide monomer, temperature-resistant anti-salt monomer, surface active function monomer and water are mixed to form comonomer water
Solution, adjusts pH to 5-10 with inorganic alkaline compound, controls -10 DEG C to 20 DEG C of solution temperature；
（2）To in comonomer aqueous solution, logical nitrogen carries out deoxygenation, controls oxygen content in solution to be less than 1mg/L, preferably little
In 0.2mg/L；
（3）Under logical condition of nitrogen gas, add composite initiation system to monomer solution, carry out adiabatic polymerisation, obtain copolymerization
Thing gel；
（4）Copolymer gel is carried out a pelletize, hydrolysis, secondary granulation, drying, pulverizing and screening and obtains temperature-resistant anti-salt
Acrylamide copolymer product.
According to the present invention, step（1）In, described temperature-resistant anti-salt monomer is monomer F of the present invention, described surface activity work(
Monomer G of the present invention can be by monomer, described inorganic alkaline compound is used for adjusting acrylamide and temperature-resistant anti-salt monomer water
The pH value of solution.Described inorganic alkaline compound can be at least one in sodium hydroxide, potassium hydroxide and sodium carbonate, preferably
For sodium hydroxide.
Present invention also offers the acrylamide copolymer being obtained according to said method.
Additionally, present invention also offers application in oil displacement agent for the described acrylamide copolymer.
Below, by following examples, the present invention will be described in more detail
In following examples, the performance test of product is carried out using following methods：
1st, method according to specified in People's Republic of China's oil and gas industry standard SY/T5862-2008 measures
The solid content of polymer, dissolution time, filtration ratio, AM residual monomer content and intrinsic viscosity.
2nd, polymer viscosity-average molecular weight method according to specified in SY/T5862-2008, using formula M=([η]/
0.000373)1.515To calculate, wherein, M is viscosity-average molecular weight, and [η] is intrinsic viscosity.
3rd, the apparent viscosity of polymer solution is, with the saline of salinity 32000mg/L, polymer is made into 1500mg/L's
Solution, with Brookfield viscometer at 95 DEG C, 7.34s-1Under the conditions of measure.
In following examples, acrylamide is commercially available from Bao Mo biochemical industry limited company, 2- acrylamido -2- first
, commercially available from Xiamen Changtian Enterprise Co., Ltd., 2,2'- azo diisobutyl amidine dihydrochlorides are public commercially available from Aldrich for base propane sulfonic acid
Department.Formula（15）The surface active function monomer of shown structure is obtained according to the method described in CN101327413A.
Embodiment 1
The present embodiment is used for the preparation method of the acrylamide copolymer of present invention offer is described
Add 1000 grams of acrylamides, 10 grams of 2- acrylamide-2-methylpro panesulfonic acids in beaker, 10 grams as formula（15）
The surface active function monomer of described structure（N ' is 2, R for 10, m '14' it is dodecyl）With 4080 grams of deionized waters, stir
Under state, control 5 DEG C of solution temperature with chilled brine, add sodium hydroxide to adjust pH to 7.Monomer solution is transferred to polymerization bottle
In, add 10.2 milligrams of 2,2'- azo diisobutyl amidine dihydrochlorides and 10.2 milligrams of N, N, N ', N '-tetramethylethylenediamine, leads to
High pure nitrogen deoxygenation 0.5 hour, adds 10.2 milligrams of sodium sulfitees and 10.2 milligrams of Ammonium persulfate .s, continues logical nitrogen until gathering
Close thermocouple in bottle to start to warm up, 8 hours response time.Colloid is taken out, becomes the copolymer of 4-6 millimeter by granulator granulation
Micelle.By degree of hydrolysis 20%, the copolymer obtaining micelle is mediated with the sodium hydroxide grain alkali of respective amount and contacts, in 90 DEG C of temperature
Lower hydrolysis 0.5 hour, after secondary granulation, is dried, by crushing and screening the product obtaining 20-80 mesh.The propylene obtaining
The performance of amide copolymer product is listed in Table 1 below.Calculated according to inventory and determine, in acrylamide copolymer, construction unit A,
The mass ratio of construction unit B, construction unit C and construction unit D is 1：0.013：0.013：0.333.
Comparative example 1
Adopt same process condition with embodiment 1, except that, it is added without as formula（15）The surface activity of shown structure
Function monomer（N ' is 2, R for 10, m '14' it is dodecyl）, thus obtaining the product of acrylamide copolymer, its performance arranges
In table 1.
Embodiment 2
The present embodiment is used for the preparation method of the acrylamide copolymer of present invention offer is described
Add 1000 grams of acrylamides, 1000 grams of 2- acrylamide-2-methylpro panesulfonic acids in beaker, 100 grams as formula
（15）The surface active function monomer of shown structure（N ' is 2, R for 10, m '14' it is dodecyl）With 4900 grams of deionized waters,
Under stirring, control 15 DEG C of solution temperature with chilled brine, add sodium hydroxide to adjust pH to 7.Monomer solution is transferred to
In polymerization bottle, add 1.05 grams of 2,2'- azo diisobutyl amidine dihydrochlorides and 1.05 grams of N, N, N ', N '-tetramethylethylenediamine,
Logical high pure nitrogen deoxygenation 0.5 hour, adds 1.05 grams of sodium sulfitees and 1.05 grams of Ammonium persulfate .s, continues logical nitrogen until being polymerized
In bottle, thermocouple starts to warm up, 4 hours response time.Colloid is taken out, becomes the copolymer glue of 4-6 millimeter by granulator granulation
Grain.By degree of hydrolysis 20%, the copolymer obtaining micelle is mediated with the sodium hydroxide grain alkali of respective amount and contacts, under temperature 70 C
Hydrolysis 4 hours, after secondary granulation, is dried, by crushing and screening the product obtaining 20-80 mesh.The acrylamide obtaining
The performance of copolymer product is listed in Table 1 below.Calculated according to inventory and determine, in acrylamide copolymer, construction unit A, structure
The mass ratio of unit B, construction unit C and construction unit D is 1：1.370：0.137：0.489.
Embodiment 3
The present embodiment is used for the preparation method of the acrylamide copolymer of present invention offer is described
Add 1000 grams of acrylamides, 100 grams of 2- acrylamide-2-methylpro panesulfonic acids in beaker, 50 grams as formula
（15）Body structure surface active function monomer（N ' is 2, R for 10, m '14' it is dodecyl）With 3450 grams of deionized waters, stir shape
Under state, control 10 DEG C of solution temperature with chilled brine, add sodium hydroxide to adjust pH to 7.Monomer solution is transferred to polymerization bottle
In, add 115 milligrams of 2,2'- azo diisobutyl amidine dihydrochlorides and 115 milligrams of N, N, N ', N '-tetramethylethylenediamine, leads to height
Pure nitrogen gas deoxygenation 0.5 hour, adds 115 milligrams of sodium sulfitees and 115 milligrams of Ammonium persulfate .s, continues logical nitrogen up to polymerization bottle
Middle thermocouple starts to warm up, 6 hours response time.Colloid is taken out, becomes the copolymer glue of 4-6 millimeter by granulator granulation
Grain.By degree of hydrolysis 20%, the copolymer obtaining micelle is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at 80 DEG C of temperature
Hydrolysis 2 hours, after secondary granulation, is dried, by crushing and screening the product obtaining 20-80 mesh.The acrylamide obtaining
The performance of copolymer product is listed in Table 1 below.Calculated according to inventory and determine, in acrylamide copolymer, construction unit A, structure
The mass ratio of unit B, construction unit C and construction unit D is 1：0.126：0.063：0.347.
Embodiment 4
The present embodiment is used for the preparation method of the acrylamide copolymer of present invention offer is described
1000 grams of acrylamides are added in beaker（AM）, 100 grams of 2- acrylamide-2-methylpro panesulfonic acids, 50 grams such as
Formula（15）The surface active function monomer of shown structure（N ' is 2, R for 10, m '14' it is cetyl）With 3450 grams of deionized waters,
Under stirring, control 10 DEG C of solution temperature with chilled brine, add sodium hydroxide to adjust pH to 7.Monomer solution is transferred to
In polymerization bottle, add 115 milligrams of 2,2'- azo diisobutyl amidine dihydrochlorides and 115 milligrams of N, N, N ', N '-tetramethyl second two
Amine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium sulfitees and 115 milligrams of Ammonium persulfate .s, continue logical nitrogen straight
To polymerization bottle, thermocouple starts to warm up, 6 hours response time.Colloid is taken out, being total to of 4-6 millimeter is become by granulator granulation
Polymers micelle.By degree of hydrolysis 20%, the copolymer obtaining micelle is mediated with the sodium hydroxide grain alkali of respective amount and contacts, in temperature
Hydrolyze 2 hours at 80 DEG C, after secondary granulation, be dried, by crushing and screening the product obtaining 20-80 mesh.Third obtaining
The performance of acrylamide copolymer product is listed in Table 1 below.Calculated according to inventory and determine, in acrylamide copolymer, construction unit
A, the mass ratio of construction unit B, construction unit C and construction unit D are 1：0.126：0.063：0.347.
Embodiment 5
The present embodiment is used for the preparation method of the acrylamide copolymer of present invention offer is described
Add 1000 grams of acrylamides, 100 grams of 2- acrylamide-2-methylpro panesulfonic acids in beaker, 50 grams as formula
（15）Body structure surface active function monomer（N ' is 2, R for 10, m '14' it is octadecyl）With 3450 grams of deionized waters, stirring
Under, control 10 DEG C of solution temperature with chilled brine, add sodium hydroxide to adjust pH to 7.Monomer solution is transferred in polymerization bottle,
Add 115 milligrams of 2,2'- azo diisobutyl amidine dihydrochlorides and 115 milligrams of N, N, N ', N '-tetramethylethylenediamine, leads to high-purity
Nitrogen deoxygenation 0.5 hour, adds 115 milligrams of sodium sulfitees and 115 milligrams of Ammonium persulfate .s, continues logical nitrogen up in polymerization bottle
Thermocouple starts to warm up, 6 hours response time.Colloid is taken out, becomes the copolymer micelle of 4-6 millimeter by granulator granulation.
By degree of hydrolysis 20%, the copolymer obtaining micelle is mediated with the sodium hydroxide grain alkali of respective amount and contact, hydrolysis at 80 DEG C of temperature
2 hours, after secondary granulation, it is dried, by crushing and screening the product obtaining 20-80 mesh.The acrylamide copolymerization obtaining
The performance of produce product is listed in Table 1 below.Calculated according to inventory and determine, in acrylamide copolymer, construction unit A, construction unit
The mass ratio of B, construction unit C and construction unit D is 1：0.126：0.063：0.347.
Embodiment 6
1000 grams of acrylamides are added in beaker（AM）, 50 grams of 2- acrylamide-2-methylpro panesulfonic acid, 50 grams of N, N-
DMAA, 50 grams as formula（15）The surface active function monomer of shown structure（N ' is 2, R for 10, m '14' it is positive ten
Dialkyl group）With 3450 grams of deionized waters, under stirring, control 10 DEG C of solution temperature with chilled brine, add sodium hydroxide to adjust
Section pH to 7.Monomer solution is transferred in polymerization bottle, adds 115 milligrams of 2,2'- azo diisobutyl amidine dihydrochlorides and 115
Milligram N, N, N ', N '-tetramethylethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium sulfitees and 115 millis
Gram Ammonium persulfate., continues logical nitrogen until thermocouple starts to warm up in polymerization bottle, 6 hours response time.Colloid is taken out, passes through
Granulator granulation becomes the copolymer micelle of 4-6 millimeter.By degree of hydrolysis 20%, by the hydrogen-oxygen of the copolymer obtaining micelle and respective amount
Change sodium grain alkali and mediate contact, hydrolyze 2 hours at 80 DEG C of temperature, after secondary granulation, be dried, obtained by crushing and screening
The product of 20-80 mesh.The performance of the acrylamide copolymer product obtaining is listed in Table 1 below.Calculated according to inventory and determine, propylene
In amide copolymer, construction unit A, the mass ratio of construction unit B, construction unit C and construction unit D are 1：0.063：0.063：
0.355.
Embodiment 7
Using process conditions same as Example 6, except that, replaced with the vinyl pyrrolidone of equal mass
N,N-DMAA, thus obtaining acrylamide copolymer product, its performance is as shown in table 1.Calculated according to inventory
Determine, in acrylamide copolymer, construction unit A, the mass ratio of construction unit B, construction unit C and construction unit D are 1：
0.063：0.063：0.355.
Embodiment 8
Using the same process condition with embodiment 2, except that, replace 2- acryloyl with the acrylic acid of equal mass
Amido -2- methyl propane sulfonic acid, and without hydrolysis, do not carry out in embodiment 2 by the copolymer obtaining micelle and hydrogen
Sodium oxide grain alkali mediates contact, the hydrolysis step of 2 hours at 80 DEG C, thus obtaining acrylamide copolymer product, its performance
As shown in table 1.Calculated according to inventory and determine, in acrylamide copolymer, construction unit A, construction unit B and construction unit C
Mass ratio be 1：1：0.1.
Embodiment 9
Using process conditions same as Example 2, except that, without hydrolysis, do not carry out in embodiment 2
The copolymer obtaining micelle is mediated with sodium hydroxide grain alkali and contacts, the hydrolysis step of 2 hours at 80 DEG C, thus obtain propylene
The product of amide copolymer, its performance is listed in Table 1 below.Calculated according to inventory and determine, in acrylamide copolymer, construction unit
The mass ratio of A, construction unit B and construction unit C is 1：1：0.1.
Table 1
Data in conjunction with table 1 understands, the molecular weight of the acrylamide copolymer product that embodiment 1 obtains can reach 3760
Ten thousand, and the molecular weight that comparative example 1 obtains acrylamide copolymer product is only 26,100,000, embodiment 1 is compared with being total to that comparative example 1 obtains
Polymers molecular weight improves nearly 11,500,000, and corresponding 95 DEG C of apparent viscosities improve 14.9mPa s.Surface activity work(in the present invention is described
The introducing of energy monomer is more beneficial for improving the apparent viscosity of copolymer solution under the molecular weight of copolymer and hot conditionss.
By embodiment 2 compared with Example 9, the molecular weight obtaining acrylamide copolymer product in embodiment 9 is 3300
Ten thousand, 95 DEG C of corresponding meter observing viscosity 18.2mPa s, both of which is less than the result of the products obtained therefrom of embodiment 2.Illustrate in copolymer
It is suitably introduced into sodium acrylate construction unit in structure to be more beneficial for improving the copolymer under the molecular weight and hot conditionss of copolymer
The apparent viscosity of solution.
Taking embodiment 1 as a example, the temperature-resistant anti-salt acrylamide copolymer that the present invention obtains is in high salinity
32000mg/L, under the conditions of 95 DEG C of high temperature, solution sees viscosity up to 28.0mPa s, and commercially available high-molecular-weight poly third
Acrylamide solution apparent viscosity is only 9.0mPa s, relatively contrasts commercially available prod, and the acrylamide copolymer of the present invention has significantly
Thickening advantage.Accordingly it is known that the acrylamide copolymer that the present invention provides has good temperature-resistant anti-salt performance.
Claims (19)
1. a kind of acrylamide copolymer it is characterised in that this acrylamide copolymer contain construction unit A, construction unit B and
Construction unit C, wherein, described construction unit A is the unit with structure shown in formula (1), and described construction unit B is to have formula
(2) at least one in the unit of structure shown in-formula (5), described construction unit C is the unit with structure shown in formula (6), institute
State acrylamide copolymer and also contain construction unit D, described construction unit D is the unit with structure shown in formula (7), and described
Construction unit A, the mass ratio of described construction unit B, described construction unit C and described construction unit D are 1：0.001-3：
0.001-0.5：0.1-1；The viscosity-average molecular weight of described acrylamide copolymer is 31,000,000-3,900 ten thousand,
Wherein, R1、R2、R6、R7、R10、R11And R12It is each independently the alkyl of hydrogen or C1-C4, R3Alkylidene for C1-C14；
R4、R5、R8、R9And R13It is each independently the alkyl of C1-C4, R14Alkyl for C1-C18, M1And M2It is each independently H, Na
With at least one in K, n is arbitrary integer in 1-20, and m is arbitrary integer, M in 1-203For potassium or sodium.
2. acrylamide copolymer according to claim 1, wherein, the viscosity-average molecular weight of described acrylamide copolymer is
34000000-3,800 ten thousand.
3. acrylamide copolymer according to claim 2, wherein, described construction unit A, described construction unit B, described
The mass ratio of construction unit C and described construction unit D is 1：0.01-1.5：0.01-0.2：0.1-1.
4. the acrylamide copolymer according to any one in claim 1-3, wherein, described construction unit B is to have
At least one in formula (2) and the unit of structure shown in (4), and R2And R7It is each independently hydrogen or methyl, R3For C1-C4's
Alkylidene, M1For sodium；In described construction unit C, R13For methyl, R14Alkyl for C5-C18, M2For sodium, n is appointing in 8-12
The integer of meaning, m is the arbitrary integer in 2-8.
5. a kind of preparation method of acrylamide copolymer, this preparation method comprises the following steps, in solution polymerization condition
Under, in the presence of initiator, make a kind of monomer mixture carry out polyreaction in water it is characterised in that described monomer mixes
Thing contains monomer E, monomer F and monomer G, and described monomer E is the monomer with structure shown in formula (8), and described monomer F is to have formula
(9) at least one in the monomer of structure shown in-formula (12), described monomer G is the monomer with structure shown in formula (13), and institute
The mass ratio stating monomer E, described monomer F and described monomer G is 1：0.001-3：0.001-0.5；Described solution polymerization bar
It is 31,000,000-3,900 ten thousand that part makes the viscosity-average molecular weight of resulting polymers after polyreaction,
Wherein, R1’、R2’、R6’、R7’、R10’、R11' and R12' it is each independently the alkyl of hydrogen or C1-C4, R3' for C1-C14
Alkylidene；R4’、R5’、R8’、R9' and R13' it is each independently the alkyl of C1-C4, R14' for C1-C18 alkyl, M1' and M2’
It is each independently at least one in H, Na and K, n ' is arbitrary integer in 1-20, m ' is arbitrary integer in 1-20；
Methods described also includes resulting polymers after polyreaction being hydrolyzed and being dried, and the process of described hydrolysis is included water
Solution agent and polymer reaction, it is 10-30% that the consumption of described hydrolytic reagent makes the degree of hydrolysis of acrylamide copolymer, described hydrolysis
Agent is selected from one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
6. method according to claim 5, wherein, the mass ratio of described monomer E, described monomer F and described monomer G is 1：
0.01-1.5：0.01-0.2；After described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is
34000000-3,800 ten thousand.
7. method according to claim 5, wherein, described monomer F is to have formula (9) and the monomer of structure shown in formula (11)
In at least one, and R2' and R7' it is each independently hydrogen or methyl, R3' for C1-C4 alkylidene, M1' it is sodium；Described list
In body G, R13' it is methyl, R14' for C5-C18 alkyl, M2' it is sodium, n ' is the arbitrary integer in 8-12, and m ' is in 2-8
Arbitrary integer.
8. method according to claim 5, wherein, when described solution polymerization starts, the weight of described monomer mixture
Amount is 0.15-0.4 with the ratio of water and the gross weight of monomer mixture：1.
9. method according to claim 8, wherein, when described solution polymerization starts, the weight of described monomer mixture
Amount is 0.2-0.3 with the ratio of water and the gross weight of monomer mixture：1.
10. method according to claim 5, wherein, described initiator is selected from azo series initiators and redox system draws
Send out agent, the consumption of described azo series initiators is 0.0001-0.1 weight % of the gross weight of monomer in monomer mixture, described
The consumption of oxidoreduction series initiators is 0.0002-0.3 weight % of the gross weight of monomer in monomer mixture；Described azo system
Initiator is water-soluble azo series initiators, and described oxidoreduction series initiators include Oxidizing and Reducing Agents, described reducing agent
For inorganic reducing agent and/or organic reducing agent, and the weight of described oxidant and described reducing agent is than for 0.1-1:1.
11. methods according to claim 10, wherein, it is different that described water-soluble azo series initiators are selected from 2,2'- azo two
Double (the 4- cyano group penta of butyl amidine dihydrochloride, 2,2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride and 4,4'- azo
Acid) at least one；Described oxidant is selected from benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- diformazan
At least one in -2,5 pairs, base (hydrogen peroxide) hexane, Ammonium persulfate., sodium peroxydisulfate and potassium peroxydisulfate；Described inorganic reducing agent
Selected from ferrous sulfate, Ferrous ammonium sulfate, Cu-lyt., potassium sulfite, sodium sulfite, ammonium bisulfite, Potassium acid sulfite, thio
At least one in sodium sulfate, Potassium hyposulfite., rongalite and sodium sulfite；Described organic reducing agent is selected from N, N- dimethyl
Ethanolamine, N, N- lupetazin, tetramethylurea, N, N dimethyl-ethylenediamine and N, N, N ', in N '-tetramethylethylenediamine extremely
Few one kind.
12. methods according to claim 5, wherein, described solution polymerization is carried out in the presence of an inert gas, described
Polymeric reaction condition includes：Temperature is -10 DEG C to 20 DEG C, and the time is 2-12 hour, and pH value is 4-12.
13. methods according to claim 12, wherein, described polymeric reaction condition includes：Temperature is 5 DEG C to 15 DEG C, when
Between be 4-8 hour, pH value be 5-10.
14. methods according to claim 5, wherein, described hydrolysising condition includes：Temperature is 50-110 DEG C, and the time is
0.5-6 hour.
15. methods according to claim 14, wherein, described hydrolysising condition includes：Temperature is 70-90 DEG C, and the time is 1-4
Hour.
16. methods according to claim 5, wherein, methods described also includes resulting polymers after hydrolysis are carried out
It is dried, the condition of described drying includes：Temperature is 40-120 DEG C, and the time is 0.2-4 hour.
17. methods according to claim 16, wherein, the condition of described drying includes：Temperature is 70-90 DEG C, and the time is
0.5-2 hour.
The acrylamide copolymer that in 18. claim 5-17, the method described in any one is obtained.
In 19. claim 1-4 and 18, the acrylamide copolymer described in any one is as the application of oil displacement agent.
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